Method for treating surfaces of textiles and non-textiles, in such a way as to stimulate the detachment of dirt

ABSTRACT

A process for the soil release treatment of surfaces of textile and nontextile materials, in which cationically modified hydrophilic nanoparticles based on uncrosslinked polymers of  
     (a) 60 to 100% by weight of one or more carboxyl-containing ethylenically unsaturated monomers or salts thereof,  
     (b) 0 to 40% by weight of one or more water-insoluble monoethylenically unsaturated monomers,  
     (c) 0 to 25% by weight of one or more sulfonic acid- and/or phosphonic acid-containing monomers or salts thereof,  
     (d) 0 to 30% by weight of one or more water-soluble nonionic monomers  
     are applied to the surface of the materials from an aqueous dispersion, where the dispersion of the hydrophilic nanoparticles can be stabilized with anionic, nonionic and/or betainic emulsifiers and/or protective colloids, and where the hydrophilic nanoparticles have a particle size of from 10 nm to 2 μm and have been cationically modified by coating their surface with one or more cationic polymers, one or more polyvalent metal ions and/or one or more cationic surfactants.

[0001] The invention relates to a process for the soil release treatmentof surfaces of textile and nontextile materials using cationicallymodified hydrophilic nanoparticles, to the cationically modifiedhydrophilic nanoparticles themselves, to aqueous dispersions comprisingsaid particles, to the use of the hydrophilic nanoparticles and to thecationically modified hydrophilic nanoparticles as soil release additiveto rinse, care, washing and cleaning compositions, and to compositionsfor the soil release treatment of surfaces.

[0002] Dispersions of particles of hydrophobic polymers, in particularaqueous dispersions of synthetic polymers and of waxes are used in theart in order to modify the properties of surfaces. For example, aqueousdispersions of finely divided hydrophobic polymers are used as bindersin paper coating slips for the coating of paper, or as coatingcompositions.

[0003] The dispersions applied in each case to a substrate in accordancewith customary methods, e.g. by knife coating, painting, immersion orimpregnation, are dried. During this, the dispersely distributedparticles form a continuous film on the respective surface.

[0004] In contrast, aqueous washing, rinse, cleaning and care processesare usually carried out in a heavily diluted liquor, where theingredients of the formulation used in each case for the most part donot remain on the substrate, but instead are disposed of with thewastewater. The modification of surfaces with dispersed hydrophobicparticles is possible in the abovementioned processes only to anentirely unsatisfactory degree. Thus, for example, U.S. Pat. No.3,580,853 discloses a laundry detergent formulation which comprises awater-insoluble finely divided substance, such as biocides and certaincationic polymers, which increase the deposition and retention of thebiocides on the surfaces of the ware.

[0005] U.S. Pat. No. 3,993,830 discloses the application of anonpermanent soil repellent finish on a textile ware by treating thetextile ware with a dilute aqueous solution which comprises apolycarboxylate and a water-soluble salt of a polyvalent metal. Suitablepolycarboxylates are, preferably, water-soluble copolymers ofethylenically unsaturated monocarboxylic acids and alkyl acrylates. Themixtures are used in domestic textile washing in the rinse cycle of thewashing machine.

[0006] U.S. Pat. No. 3,782,898 discloses the application of anonpermanent soil repellent finish to a textile ware by treating thetextile ware with an acidic dilute aqueous solution which comprises anacrylate polymer in dissolved or emulsified form. The specificationgives no information regarding an advantageous use of particulatepolymers and, in particular, no information regarding an advantageouscombination of particulate polymers with cationic substances.

[0007] It is an object of the present invention to provide an improvedprocess for the soil release modification of textile surfaces, leather,hard smooth surfaces and hard porous surfaces.

[0008] We have found that this object is achieved according to theinvention by a process for the soil release treatment of surfaces oftextile and nontextile materials, in which cationically modifiedhydrophilic nanoparticles based on uncrosslinked polymers of

[0009] (a) 60 to 100% by weight of one or more carboxyl-containingethylenically unsaturated monomers or salts thereof,

[0010] (b) 0 to 40% by weight of one or more water-insolublemonoethylenically unsaturated monomers,

[0011] (c) 0 to 25% by weight of one or more sulfonic acid- and/orphosphonic acid-containing monomers or salts thereof,

[0012] (d) 0 to 30% by weight of one or more water-soluble nonionicmonomers

[0013] are applied to the surface of the materials from an aqueousdispersion, where the dispersion of the hydrophilic nanoparticles can bestabilized with anionic, nonionic and/or betainic emulsifiers and/orprotective colloids, and where the hydrophilic nanoparticles have aparticle size of from 10 nm to 2 μm and have been cationically modifiedby coating their surface with one or more cationic polymers, one or morepolyvalent metal ions and/or one or more cationic surfactants.

[0014] We have found that this object is further achieved by the use ofthe hydrophilic nanoparticles and the cationically modified hydrophilicnanoparticles, and the aqueous dispersions comprising the hydrophilic orcationically modified hydrophilic nanoparticles as soil release additiveto rinse, care, washing and cleaning compositions.

[0015] The invention also provides the cationically modified hydrophilicnanoparticles themselves, and the aqueous dispersions comprising saidparticles.

[0016] For the purposes of the present invention, hydrophilicnanoparticles are hydrophilic polymer particles of uncrosslinkedpolymers or particulate hydrogels of uncrosslinked polymers whoseparticle size is 10 nm to 2 μm and which can be bonded to the surface tobe modified by means of cationic components. Particulate hydrogels isthe term used to refer to polymer particles highly swollen with water,the acid groups of the polymer particles optionally being partiallyneutralized with water-soluble bases such as LiOH, NaOH, KOH or ammoniumhydroxides. Suitable cationic components are cationic polymers,polyvalent metal cations or cationic surfactants. Cationically modifiedhydrophilic nanoparticles for the purposes of the invention have acoating on their surface with one or more of said cationic components.

[0017] The hydrophilic nanoparticles to be used according to theinvention are obtained in the preparation firstly in the form of aqueousdispersions and can, optionally after concentration or dilution, be usedas such. The hydrophilic nanoparticles can, after spray drying, also beobtained and used as a solid. From the aqueous dispersions of thehydrophilic nanoparticles, it is possible to obtain aqueous dispersionsof the cationically modified hydrophilic nanoparticles by adding thecationic components, and to use them as such, or, after spray drying,the cationically modified hydrophilic nanoparticles can be obtained andused as a solid. The cationically modified hydrophilic nanoparticles canalso be formed only under the conditions of use in an aqueous rinse,care, washing and cleaning liquor.

[0018] The cationically modified hydrophilic nanoparticles areobtainable, for example, by mixing aqueous dispersions of thehydrophilic nanoparticles with an aqueous solution or dispersion of thecationic polymers, of the polyvalent metal cations in the form of theirsoluble salts or the cationic surfactants. The cationic component ispreferably used in the form of aqueous solutions, but it is alsopossible to use aqueous dispersions of the cationic polymers whosedispersed particles have an average diameter up to 2 μm. The twocomponents are usually mixed at room temperature, although mixing canalso be carried out at temperatures of, for example, 0° to 100° C.,provided that the dispersions do not coagulate upon heating.

[0019] The hydrophilic nanoparticles to be used according to theinvention are insoluble in water at the application pH. In the aqueousdispersion, they are in the form of particles or particulate hydrogelswith an average particle size of from 10 nm to 2 μm, preferably 25 nm to1 μm, particularly preferably 40 nm to 800 nm and in particular 100 to600 nm, and can be obtained from the aqueous dispersions as powders. Theaverage particle size of the nanoparticles can be determined, forexample, under the electron microscope or using light scatteringexperiments.

[0020] The pH of the aqueous dispersions of the hydrophilicnanoparticles is, generally, 1 to 6.5 and is preferably in the rangefrom 1.5 to 5.5, particularly preferably in the range from 2 to 4.5.

[0021] The hydrophilic nanoparticles to be used according to theinvention usually exhibit a pH-dependent solubility and swellingbehavior. The swelling behavior is dependent on the monomer composition,the average molecular weight of the polymers and the temperature. At apH below 6.5, preferably below 5.5, particularly preferably below 4.5,the particles are water-insoluble and retain their particulate characteror particulate hydrogel character upon dispersion in concentrated and indilute aqueous media. By contrast, the hydrophilic nanoparticles usedaccording to the invention swell greatly, or partially or completelydissolve in water under neutral, in particular under alkaline,conditions.

[0022] Nanoparticles used according to the invention containuncrosslinked polymers of

[0023] (a) 60 to 100% by weight, preferably 70 to 99% by weight,particularly preferably 75 to 95% by weight, of one or morecarboxyl-containing ethylenically unsaturated monomers or salts thereof,

[0024] (b) 0 to 40% by weight, preferably 1 to 30% by weight,particularly preferably 5 to 25% by weight, of one or morewater-insoluble monoethylenically unsaturated monomers,

[0025] (c) 0 to 25% by weight, preferably 0 to 15% by weight,particularly preferably 0.1 to 5% by weight, of one or more sulfonicacid- and/or phosphonic acid-containing monomers of salts thereof,

[0026] (d) 0 to 30% by weight, preferably 0 to 20% by weight,particularly preferably 0 to 10% by weight, of one or more water-solublenonionic monomers.

[0027] Preferred carboxyl-containing ethylenically unsaturated monomersa) are α,β-unsaturated C₃-C₆-carboxylic acids, such as acrylic acid,methacrylic acid, ethacrylic acid, crotonic acid, vinylacetic acid,itaconic acid, maleic acid, itaconic monoesters of C₁-C₆-alcohols,maleic acid or maleic monoesters of C₁-C₆-alcohols. Particularpreference is given to acrylic acid, methacrylic acid, maleic acid ormaleic monoesters of C₁-C₆-alcohols. Special preference is given tomethacrylic acid.

[0028] Water-insoluble monomers b) are all monomers which are soluble inwater at room temperature in an amount of less than 50 g/l. These aremonomers from the group of the alkyl esters of monoethylenicallyunsaturated C₃-C₆-carboxylic acids and monohydric C₁-C₂₂-alcohols,hydroxyalkyl esters of monoethylenically unsaturated C₃-C₅-carboxylicacids and dihydric C₂-C₄-alcohols, vinyl esters of saturatedC₁-C₁₈-carboxylic acids, ethylene, propylene, isobutylene,C₄-C₂₄-alpha-olefins, butadiene, styrene, alpha-methylstyrene,acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidenefluoride, fluoroethylene, chlorotrifluoroethylene, hexafluoropropene,esters and amides of C₃-C₅-monoethylenically unsaturated carboxylicacids with perfluoroalkyl-containing alcohols or amines, allyl and vinylesters of perfluoroalkyl-containing carboxylic acids, or mixturesthereof. Higher proportions of water-insoluble monomers b) arepreferably present in the polymers if very polar monomers a), such asacrylic acid, itaconic acid and maleic acid, or monomers c) or d) arepresent in the polymer in a relatively large amount, for example in anamount above 10% by weight, in particular above 20% by weight.

[0029] Preferred water-insoluble monomers b) are acrylonitrile, methylacrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate,tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate,hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate,(meth)acrylate of perfluoroalkyl-substituted alcoholsCF₃—(C₂F₄)_(n)—(CH₂)_(m)—OH or C₂F₅—(C₂F₄)_(n)—(CH₂)_(m)—OH where n=2-8,m=1 or 2, vinyl acetate, vinyl propionate, styrene, ethylene, propylene,butylene, isobutene, diisobutene and tetrafluoroethylene, andparticularly preferred water-insoluble monomers b) are methyl acrylate,methyl methacrylate, ethyl acrylate, n-butyl acrylate, tert-butylacrylate and vinyl acetate.

[0030] Suitable sulfonic acid- or phosphonic acid-containing monomers d)are, for example, acrylamido-2-methylpropanesulfonic acid, vinylsulfonicacid, methallylsulfonic acid, vinylphosphonic acid, and the alkali metaland ammonium salts of these monomers.

[0031] Suitable water-soluble monomers d) have a solubility of at least50 μl of water at room temperature. Suitable monomers d) are, forexample, acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide,N-vinylpyrrolidone, N-vinyloxazolidone, methyl polyglycol acrylate,methyl polyglycol methacrylate and methyl polyglycol acrylamide.Preferred monomers d) are vinylpyrrolidone, acrylamide andN-vinylformamide.

[0032] A characteristic feature of the uncrosslinked polymers present inthe nanoparticles is their particulate, i.e. undissolved, characterunder the conditions of use. This particulate character is given at a pHbelow 6.5, preferably below 5.5, particularly preferably below 4.5 formost of the compositions. In cases where the proportions of readilywater-soluble monomers a), c) or d) are high, it may be necessary tofurther reduce the pH during use, e.g. below 3 or below 2, in order toensure the particulate character. In the case of very small particles inthe range from 10-100 nm, it may only be possible to detect theparticles in some circumstances using specific techniques, such aselectron microscopy.

[0033] Uncrosslinked polymers of the monomers a), and optionally b), c)and/or d) can be prepared by the known processes of solutionpolymerization, precipitation polymerization, suspension polymerizationor emulsion polymerization of the monomers using free-radicalpolymerization initiators. The hydrophilic nanoparticles are preferablyobtained by the process of emulsion polymerization in water. Thepolymers have, for example, molar masses of from 1 000 to 5 000 000,preferably from 5 000 to 1 000 000; the molar masses of the polymers aremost often in the range from 10 000 to 500 000.

[0034] Apart from said polymerization processes, other processes for thepreparation of the hydrophilic nanoparticles are also suitable. Thus,for example, it is possible to precipitate out polymers by lowering thesolubility of the polymers in the solvent. Such a method consists, forexample, in dissolving an acidic group-containing polymer in a suitablewater-miscible solvent, and metering in water in an excess such that thepH of the initial charge is lower by at least 1 than the equivalent pHof the polymers. Equivalent pH is understood as meaning the pH at which50% of the acid groups of the polymer have been neutralized. In thisprocess, it may be necessary to add a dispersion auxiliary, pHregulators and/or salts in order to obtain stable finely divideddispersions.

[0035] The aqueous dispersions of the hydrophilic nanoparticles can bestabilized with anionic, nonionic or betainic emulsifiers and/orprotective colloids. The emulsifiers and protective colloids may bepresent as dispersion auxiliaries during the preparation of thenanoparticles, or can be added subsequently.

[0036] Examples of anionic emulsifiers are anionic surfactants andsoaps. Anionic surfactants which may be used are alkyl and alkenylsulfates, sulfonates, phosphates and phosphonates, alkyl- andalkenylbenzenesulfonates, alkyl ether sulfates and phosphates, saturatedand unsaturated C₁₀-C₂₅-carboxylic acids and salts thereof.

[0037] Nonionic and/or betainic emulsifiers can also be used. Adescription of suitable emulsifiers is given, for example, in HoubenWeyl, Methoden der organic Chemie [Methods of organic chemistry], volumeXIV/1, Makromolekulare Stoffe [Macromolecular substances], Georg ThiemeVerlag, Stuttgart, 1961, pages 192 to 208.

[0038] Examples of anionic protective colloids are water-soluble anionicpolymers. In this connection, it is possible to use very different typesof polymer. Anionically substituted polysaccharides and/or water-solubleanionic copolymers of acrylic acid, methacrylic acid, maleic acid,maleic monoesters, vinylsulfonic acid, styrenesulfonic acid oracrylamidopropanesulfonic acid with other vinylic monomers arepreferably used. Suitable anionically substituted polysaccharides are,for example, carboxymethylcellulose, carboxymethyl starch, oxidizedstarch, oxidized cellulose and other oxidized polysaccharides, and thecorresponding derivatives of the freely degraded polysaccharides.Suitable water-soluble anionic copolymers are, for example, copolymersof acrylic acid with vinyl acetate, acrylic acid with ethylene, acrylicacid with acrylamide, acrylamidopropanesulfonic acid with acrylamide oracrylic acid with styrene.

[0039] It is also possible to use nonionic or betainic protectivecolloids. An overview of customarily used protective colloids is givenin Houben Weyl, Methoden der organischen Chemie, volume XIV/1,Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pages 411to 420.

[0040] For the preparation of dispersions of hydrophilic nanoparticles,polymers which contain only monomers a) and optionally b) can bedispersed in water at a pH below 6.5. In this connection, it is oftenadvantageous to use nonionic emulsifiers or protective colloids.

[0041] Preference is given to using polymers which contain at least onemonomer c) in copolymerized form, and/or emulsifying the polymers withat least one anionic emulsifier and/or stabilizing the dispersion withat least one anionic protective colloid.

[0042] To stabilize hydrophilic nanoparticles which contain anionicgroups and are to be used according to the invention, further polymerscan additionally be added during the dispersion. Such polymers are, forexample, polysaccharides, polyvinyl alcohols and polyacrylamides.

[0043] Hydrophilic nanoparticles can also be prepared by emulsifying amelt of the hydrophilic polymers in a controlled manner. For this, thepolymer or a mixture of the polymer with other additives is, forexample, melted, and under the action of shear forces, e.g. in anUltra-Turrax, water is metered in in an excess such that the pH of theinitial charge is lower by at least 1 than the equivalent pH of thepolymer. Here, it may in some instances be necessary to add emulsifyingauxiliaries, pH regulators and/or salts. With this variant of thepreparation of finely divided polymer dispersions, it is also possibleto co-use additional polymers such as polysaccharides, polyvinylalcohols or polyacrylamides, particularly if the hydrophilic polymercontains anionic groups.

[0044] A further method of preparing hydrophilic nanoparticles whichcontain anionic groups consists in treating aqueous, alkaline solutionsof the polymers with an acid, preferably under the action of strongshear forces.

[0045] The cationically modified, hydrophilic nanoparticles to be usedaccording to the invention are obtainable by coating the surface of thehydrophilic nanoparticles with cationic polymers, polyvalent metal ionsand/or cationic surfactants.

[0046] During the treatment of anionically adjusted dispersions of thehydrophilic nanoparticles with an aqueous solution of a cationicpolymer, the charge of the originally anionic dispersed particles ischanged, so that they have, preferably, a cationic charge after thetreatment. Thus, for example, cationically modified dispersions ofparticulate hydrophilic nanoparticles in 0.1% strength by weight aqueousdispersion at pH 4 have an interface potential of −5 to +50 mV,preferably from −2 to +25 mV, in particular from 0 to +15 mV. Theinterface potential is determined by measuring the electrophoreticmobility in dilute aqueous dispersion at the pH of the intended useliquor.

[0047] Cationic polymers which may be used are all natural or syntheticcationic polymers which contain amino and/or ammonium groups and arewater-soluble. Examples of such cationic polymers are polymerscontaining vinylamine units, polymers containing vinylimidazole units,polymers containing quaternary vinylimidazole units, condensates ofimidazole and epichlorohydrin, uncrosslinked polyamidoamines,uncrosslinked polyamidoamines grafted with ethyleneimine,polyethyleneimines, alkoxylated polyethyleneimines, uncrosslinkedpolyethyleneimines, amidated polyethyleneimines, alkylatedpolyethyleneimines, polyamines, amine-epichlorohydrin polycondensates,alkoxylated polyamines, polyallylamines, polydimethyldiallylammoniumchlorides, polymers containing basic (meth)acrylamide or (meth)acrylicester units, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units, and/or lysine condensates.

[0048] Cationic polymers are also understood as meaning amphotericpolymers which have a net cationic charge, i.e. the polymers containboth anionic and also cationic monomers in copolymerized form, but themolar proportion of the cationic units present in the polymer is greaterthan that of the anionic units.

[0049] For the preparation of polymers containing vinylamine units, thestarting materials are, for example, open-chain N-vinylcarboxamides ofthe formula (I)

[0050] in which R¹ and R² may be identical or different and are hydrogenand C₁- to C₆-alkyl. Suitable monomers are, for example,N-vinylformamide (R¹═R²═H in formula I) N-vinyl-N-methylformamide,N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide,N-vinyl-N-methylpropionamide and N-vinylpropionamide. To prepare thepolymers, said monomers can either be polymerized on their own, in amixture with one another or together with other monoethylenicallyunsaturated monomers. Preference is given to starting from homo- orcopolymers of N-vinylformamide. Polymers containing vinylamine units areknown, for example, from U.S. Pat. No. 4,421,602, EP-A-0 216 387 andEP-A-0 251 182. They are obtained by hydrolysis of polymers whichcontain the monomers of the formula I in copolymerized form with acids,bases or enzymes.

[0051] Suitable monoethylenically unsaturated monomers which arecopolymerized with the N-vinylcarboxamides are all compoundscopolymerizable therewith. Examples thereof are vinyl esters ofsaturated carboxylic acids having 1 to 6 carbon atoms, such as vinylformate, vinyl acetate, vinyl propionate and vinyl butyrate, and vinylethers, such as C₁- to C₆-alkyl vinyl ethers, e.g. methyl or ethyl vinylether. Further suitable comonomers are ethylenically unsaturated C₃- toC₆-carboxylic acids, for example acrylic acid, methacrylic acid, maleicacid, crotonic acid, itaconic acid and vinyl acetic acid, and the alkalimetal and alkaline earth metal salts thereof, esters, amides andnitriles of said carboxylic acids, for example methyl acrylate, methylmethacrylate, ethyl acrylate and ethyl methacrylate.

[0052] Further suitable monoethylenically unsaturated monomers which arecopolymerized with the N-vinylcarboxamides are carboxylic esters derivedfrom glycols or polyalkylene glycols, where in each case only one OHgroup is esterified, e.g. hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate,hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylicmonoesters of polyalkylene glycols of molar mass from 500 to 10 000.Further suitable comonomers are esters of ethylenically unsaturatedcarboxylic acids with amino alcohols, such as dimethylaminoethylacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate,diethylaminoethyl methacrylate, dimethylaminopropyl acrylate,dimethylaminopropyl methacrylate, diethylaminopropyl acrylate,dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basicacrylates can be used in the form of the free bases, the salts withmineral acids, such as hydrochloric acid, sulfuric acid or nitric acid,the salts with organic acids, such as formic acid, acetic acid;propionic acid, or the sulfonic acids, or in quaternized form. Suitablequaternizing agents are, for example, dimethyl sulfate, diethyl sulfate,methyl chloride, ethyl chloride or benzyl chloride.

[0053] Further suitable comonomers are amides of ethylenicallyunsaturated carboxylic acids, such as acrylamide, methacrylamide, andN-alkylmono- and diamides of monoethylenically unsaturated carboxylicacids having alkyl radicals of from 1 to 6 carbon atoms, e.g.N-methylacrylamide, N,N-dimethylacrylamide, N-methylmethacrylamide,N-ethylacrylamide, N-propylacrylamide and tert-butylacrylamide, andbasic (meth)acrylamides, such as, for example,dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide,diethylaminoethylacrylamide, diethylaminoethyl-methacrylamide,dimethylaminopropylacrylamide, diethyl aminopropylacrylamide,dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

[0054] Also suitable as comonomers are N-vinylpyrrolidone,N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole,and substituted N-vinylimidazoles, such as, for example,N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole,N-vinyl-5-methyl-imidazole, N-vinyl-2-ethylimidazole andN-vinylimidazolines, such as N-vinyl-imidazoline,N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. Apart frombeing used in the form of the free bases, N-vinylimidazoles andN-vinylimidazolines can also be used in a form neutralized with mineralacids or organic acids or in quaternized form, the quaternizationpreferably being effected using dimethyl sulfate, diethyl sulfate,methyl chloride or benzyl chloride. Also suitable arediallyldialkylammonium halides, such as, for example,diallyldimethylammonium chlorides.

[0055] Further suitable comonomers are monomers containing sulfo groups,such as, for example, vinylsulfonic acid, allylsulfonic acid,methallylsulfonic acid, styrenesulfonic acid, the alkali metal orammonium salts of these acids or 3-sulfopropyl acrylate, where thecontent of cationic units in the amphoteric copolymers exceeds thecontent of anionic units, meaning that the polymers have a cationiccharge overall.

[0056] The copolymers comprise, for example,

[0057] 99.99 to 1 mol %, preferably 99.9 to 5 mol %, ofN-vinylcarboxamides of the formula I and

[0058] 0.01 to 99 mol %, preferably 0.1 to 95 mol %, of othermonoethylenically unsaturated monomers copolymerizable therewith

[0059] in copolymerized form.

[0060] To prepare polymers containing vinylamine units, preference isgiven to starting from homopolymers of N-vinylformamide or of copolymersobtainable by copolymerization of

[0061] N-vinylformamide with

[0062] vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile,N-vinylcaprolactam, N-vinylurea, acrylic acid, N-vinylpyrrolidone or C₁-to C₆-alkyl vinyl ethers

[0063] and subsequent hydrolysis of the homopolymers or of thecopolymers with the formation of vinylamine units from the copolymerizedN-vinylformamide units, the degree of hydrolysis being, for example, 0.1to 100 mol %.

[0064] The hydrolysis of the above-described polymers is carried out inaccordance with known processes by the action of acids, bases orenzymes. In this process, the copolymerized monomers of the aboveformula (I) produce, as a result of cleaving off the group

[0065] where R² has the meaning given therefor in formula I, polymerswhich contain vinylamine units of the formula (III)

[0066] in which R¹ has the meaning given in formula I. If acids are usedas hydrolysis agents, the units (III) are in the form of the ammoniumsalt.

[0067] The homopolymers of the N-vinylcarboxamides of the formula (I)and their copolymers can be hydrolyzed to 0.1 to 100 mol %, preferably70 to 100 mol %. In most cases, the degree of hydrolysis of thehomopolymers and copolymers is 5 to 95 mol %. The degree of hydrolysisof the homopolymers is synonymous with the content of vinylamine unitsin the polymers. In the case of copolymers which contain vinyl esters incopolymerized form, in addition to the hydrolysis of theN-vinylformamide units, hydrolysis of the ester groups can arise withthe formation of vinyl alcohol units. This is the case particularly whenthe hydrolysis of the copolymers is carried out in the presence ofsodium hydroxide solution. Copolymerized acrylonitrile is likewisechemically changed during the hydrolysis. Here, amide groups or carboxylgroups, for example, form. The homopolymers and copolymers containingvinylamine units may optionally contain up to 20 mol % of amidine units,which is formed, for example, by the reaction of formic acid with twoadjacent amino groups or by intramolecular reaction of an amino groupwith an adjacent amide group e.g. of copolymerized N-vinylformamide. Themolar masses of the polymers containing vinylamine units are, forexample, 1 000 to 10 million, preferably 10 000 to 5 million (determinedby light scattering). This molar mass range corresponds, for example, toK values of from 5 to 300, preferably 10 to 250 (determined inaccordance with H. Fikentscher in 5% strength by weight aqueous sodiumchloride solution at 25° C. and a polymer concentration of 0.5% byweight).

[0068] The polymers containing vinylamine units are preferably used insalt-free form. Salt-free aqueous solutions of polymers containingvinylamine units can be prepared, for example, from the above-describedsalt-containing polymer solutions using ultrafiltration over suitablemembranes at cut-offs of, for example, 1 000 to 500 000 daltons,preferably 10 000 to 300 000 daltons. The aqueous solutions of otherpolymers containing amino and/or ammonium groups described below canalso be obtained in salt-free form by means of ultrafiltration.

[0069] Further suitable cationic polymers are polyethyleneimines.Polyethyleneimines are prepared, for example, by polymerization ofethyleneimine in aqueous solution in the presence of acid-eliminatingcompounds, acids or Lewis acids. Polyethyleneimines have, for example,molar masses up to 2 million, preferably from 200 to 500 000. Particularpreference is given to using polyethyleneimines having molar masses offrom 500 to 100 000. Also suitable are water-soluble, uncrosslinkedpolyethyleneimines which are obtainable by reacting polyethyleneimineswith crosslinkers, such as epichlorohydrin or bischlorohydrin ethers ofpolyalkylene glycols having 2 to 100 ethylene oxide and/or propyleneoxide units. Amidic polyethyleneimines which are obtainable, forexample, by amidation of polyethyleneimines with C₁- toC₂₂-monocarboxylic acids are also suitable. Further suitable cationicpolymers are alkylated polyethyleneimines and alkoxylatedpolyethyleneimines. During the alkoxylation, 1 to 5 ethylene oxide orpropylene oxide units are used, for example, per NH unit inpolyethyleneimine.

[0070] Further suitable amino- and/or ammonium-containing polymers arepolyamidoamines, which are obtainable, for example, by condensingdicarboxylic acids with polyamines. Suitable polyamidoamines areobtained, for example, by reacting dicarboxylic acids having 4 to 10carbon atoms with polyalkylenepolyamines which contain 3 to 10 basicnitrogen atoms in the molecule. Suitable dicarboxylic acids are, forexample, succinic acid, maleic acid, adipic acid, glutaric acid, subericacid, sebacic acid and terephthalic acid. In the preparation of thepolyamidoamines it is also possible to use mixtures of dicarboxylicacids as well as mixtures of two or more polyalkylenepolyamines.Examples of suitable polyalkylenepolyamines are diethylenetriamine,triethylenetetramine, tetraethyl enepentamine, dipropylenetriamine,tripropylenetetramine, dihexamethylenetriamine,aminopropylethylenediamine and bisaminopropylethylenediamine. For thepreparation of the polyamido amines, the dicarboxylic acids andpolyalkylenepolyamines are heated to relatively high temperatures, e.g.to temperatures in the range from 120 to 220, preferably 130 to 180° C.The water which forms during the condensation is removed from thesystem. Lactones or lactams of carboxylic acids having 4 to 8 carbonatoms may also be used in the condensation. 0.8 to 1.4 mol of apolyalkylenepolyamine, for example, are used per mole of dicarboxylicacid.

[0071] Further amino-containing polymers are polyamidoamines graftedwith ethyleneimine. They are obtainable from the above-describedpolyamidoamines by reaction with ethyleneimine in the presence of acidsor Lewis acids, such as sulfuric acid or boron trifluoride etherates, attemperatures of, for example, 80 to 100° C. Compounds of this type aredescribed, for example, in DE-B-24 34 816.

[0072] The optionally uncrosslinked polyamidoamines, which haveoptionally been additionally grafted with ethyleneimine prior tocrosslinking, are also suitable as cationic polymers. The uncrosslinkedpolyamidoamines grafted with ethyleneimine are water-soluble and have,for example, an average molecular weight of from 3 000 to 1 milliondaltons. Customary crosslinkers are, for example, epichlorohydrin orbischlorohydrin ethers of alkylene glycols and polyalkylene glycols.

[0073] Further examples of cationic polymers which contain amino and/orammonium groups are polydiallyldimethylammonium chlorides. Polymers ofthis type are likewise known.

[0074] Further suitable cationic polymers are copolymers of, forexample, 1 to 99 mol %, preferably 30 to 70 mol % of acrylamide and/ormethacrylamide and 99 to 1 mol %, preferably 70 to 30 mol % of cationicmonomers, such as dialkylaminoalkylacrylamide, dialkylaminoalkylacrylicesters and/or dialkylaminoalkylmethacrylamide and/ordialkylaminoalkylmethacrylic esters. The basic acrylamides andmethacrylamides are likewise preferably in a form neutralized with acidsor in quaternized form. Examples which may be mentioned are

[0075] N-trimethylammoniumethylacrylamide chloride,

[0076] N-trimethylammoniumethylmethacrylamide chloride,

[0077] N-trimethylammoniumethyl methacrylate chloride,

[0078] N-trimethylammoniumethyl acrylate chloride,

[0079] trimethylammoniumethylacrylamide methosulfate,

[0080] trimethylammoniumethylmethacrylamide methosulfate,

[0081] N-ethyldimethylammoniumethylacrylamide ethosulfate,

[0082] N-ethyldimethylammoniumethylmethacrylamide ethosulfate,

[0083] trimethylammoniumpropylacrylamide chloride,

[0084] trimethylammoniumpropylmethacrylamide chloride,

[0085] trimethylammoniumpropylacrylamide methosulfate,

[0086] trimethylammoniumpropylmethacrylamide methosulfate and

[0087] N-ethyldimethylammoniumpropylacrylamide ethosulfate.

[0088] Preference is given to trimethylammoniumpropylmethacrylamidechloride.

[0089] Further suitable cationic monomers for the preparation of(meth)acrylamide polymers are diallyldimethylammonium halides and basic(meth)acrylates. Suitable examples are copolymers of 1 to 99 mol %,preferably 30 to 70 mol %, of acrylamide and/or methacrylamide and 99 to1 mol %, preferably 70 to 30 mol %, of dialkylaminoalkyl acrylatesand/or methacrylates, such as copolymers of acrylamide andN,N-dimethylaminoethyl acrylate or copolymers of acrylamide anddimethylaminopropyl acrylate. Basic acrylates or methacrylates arepreferably in a form neutralized with acids or in quaternized form. Thequaternization can be carried out, for example, with methyl chloride orwith dimethyl sulfate.

[0090] Further suitable cationic polymers which have amino and/orammonium groups are polyallylamines. Polymers of this type are obtainedby homopolymerization of allylamine, preferably in a form neutralizedwith acids or in quaternized form, or by a copolymerization ofallylamine with other monoethylenically unsaturated monomers which aredescribed above as comonomers for N-vinylcarboxamides.

[0091] The cationic polymers have, for example, K values of from 8 to300, preferably 100 to 180 (determined in accordance with H. Fikentscherin 5% strength by weight aqueous sodium chloride solution at 25° C. anda polymer concentration of 0.5% by weight). At a pH of 4.5, they have,for example, a charge density of at least 1, preferably at least 4 meq/gof polyelectrolyte.

[0092] Examples of preferred cationic polymers arepolydimethyldiallylammonium chloride, polyethyleneimine, polymerscontaining vinylamine units, copolymers of acrylamide or methacrylamide,containing basic monomers in copolymerized form, polymers containinglysine units, or mixtures thereof. Examples of cationic polymers are:

[0093] copolymers of 50% vinylpyrrolidone and 50% trimethylammoniumethylmethacrylate methosulfate, M_(w) 1 000 to 500 000;

[0094] copolymers of 30% acrylamide and 70% trimethylammoniumethylmethacrylate methosulfate, M_(w) 1 000 to 1 000 000;

[0095] copolymers of 70% acrylamide and 30% dimethylaminoethylmethacrylamide, M_(w) 1 000 to 1 000 000;

[0096] copolymers of 50% hydroxyethyl methacrylate and 50%2-dimethylaminoethyl methacrylamide, Mw 1000 to 500 000;

[0097] copolymer of 70% hydroxyethyl methacrylate and 50%2-dimethyl-aminoethylmethacrylamide; copolymer of 30% vinylimidazolemethochloride, 50% dimethylaminoethyl acrylate, 15% acrylamide, 5%acrylic acid;

[0098] polylysines having an M_(w) of from 250 to 250 000, preferably500 to 100 000, and lysine cocondensates having molar masses M_(w) offrom 250 to 250 000, the cocondensible component being, for example,amines, polyamines, ketene dimers, lactams, alcohols, alkoxylatedamines, alkoxylated alcohols and/or nonproteinogenic amino acids,

[0099] vinylamine homopolymers, 1 to 99% of hydrolyzedpolyvinyl-formamides, copolymers of vinylformamide and vinyl acetate,vinyl alcohol, vinylpyrrolidone or acrylamide having molar masses offrom 3 000-500 000,

[0100] vinylimidazole homopolymers, vinylimidazole copolymers withvinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate havingmolar masses of from 5 000 to 500 000, and quaternary derivativesthereof,

[0101] polyethyleneimines, uncrosslinked polyethyleneimines or amidatedpolyethyleneimines having molar masses of from 500 to 3 000 000,

[0102] amine/epichlorohydrin polycondensates which contain, as aminecomponent, imidazole, piperazine, C₁-C₈-alkylamines, C₁-C₈-dialkylaminesand/or dimethylaminopropylamine and which have a molar mass of from 500to 250 000,

[0103] polymers containing basic (meth)acrylamide or (meth)acrylic esterunits, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units and having molar masses of from 10 000 to 2000 000.

[0104] Futhermore, it is also possible to incorporate a minor amount(<10% by weight) of anionic comonomers by polymerization, e.g. acrylicacid methacrylic acid, vinylsulfonic acid or alkali metal salts of saidacids.

[0105] In order to cationically modify hydrophilic nanoparticles, theycan also be treated with polyvalent metal ions and/or cationicsurfactants. Coating of the particles with polyvalent metal ions isachieved by, for example, adding an aqueous solution of at least onewater-soluble, polyvalent metal salt to an aqueous dispersion ofanionically dispersed hydrophilic nanoparticles, or dissolving awater-soluble, polyvalent metal salt therein, the modification of theanionically dispersed hydrophilic nanoparticles with cationic polymersbeing carried out either before, at the same time as or after thistreatment. Suitable metal salts are, for example, the water-solublesalts of Ca, Mg, Ba, Al, Zn, Fe, Cr or mixtures thereof. Otherwater-soluble heavy metal salts which are derived, for example, from Cu,Ni, Co and Mn can also in principle be used, but are not desired in allapplications. Examples of water-soluble metal salts are calciumchloride, calcium acetate, magnesium chloride, aluminum sulfate,aluminum chloride, barium chloride, zinc chloride, zinc sulfate, zincacetate, iron(II) sulfate, iron(III) chloride, chromium(III)sulfate,copper sulfate, nickel sulfate, cobalt sulfate and manganese sulfate.Preference is given to using the water-soluble salts of Ca, Al and Znfor the cationic modification.

[0106] The charge of the hydrophilic nanoparticles can also be changedusing cationic surfactants. Of potential suitability for this purposeare cationic surfactants of varying structures. An overview of aselection of suitable cationic surfactants is given in UllmansEnzyklopàdie Industriellen Chemie [Ullmanns Encyclopaedia of IndustrialChemistry], Sixth Edition, 1999, Electronic Release, Chapter“Surfactants”, Chapter 8, Cationic Surfactants.

[0107] Particularly suitable cationic surfactants are, for example C₇-to C₂₅-alkylamines, C₇- to C₂₅-N,N-dimethyl-N-(hydroxyalkyl)ammoniumsalts mono- and di-(C₇-C₂₅)alkyldimethyl-ammonium compounds quaternizedwith alkylating agents, ester quats, such as quaternary esterifiedmono-, di- or trialkanolamines which have been esterified with C₈- toC₂₂-carboxylic acids, imidazoline quats, such as 1-alkylimidazoliniumsalts of the formulae

[0108] where

[0109] R¹═C₁-C₂₅-alkyl or C₂-C₂₅-alkenyl,

[0110] R²═C₁-C₄-alkyl or hydroxyalkyl and

[0111] R³═C₁-C₄-alkyl, hydroxyalkyl or an R₁-(C═O)—X—(CH₂)_(n)— whereX═O or NH and

[0112] n=2 or 3, and

[0113] where at least one radical R¹═C₇-C₂₂-alkyl.

[0114] For many commercial applications and everyday domesticapplications, the soil release modification of textiles, textilesurfaces, leather, wood, smooth and structured hard surfaces is ofimportance. For example, suitable surfaces of textile and nontextilematerials to be treated according to the invention are microscopic hardsurfaces, floor coverings and wall coverings, glass surfaces, ceramicsurfaces, stone surfaces, concrete surfaces, metal surfaces, enameledsurfaces, plastic surfaces, wood surfaces, surfaces of coated woods orpainted surfaces. Suitable microscopic surfaces are, for example, thesurfaces of porous bodies, such as foams, woods, leather, porousconstruction materials and porous minerals.

[0115] Other suitable surfaces are floor or wall paints or coatings andcellulose fleeces. It is not always possible to carry out themodification of the surfaces by impregnation and coating processes withconcentrated formulations. It is often desirable to carry out themodification by means of a rinsing of the material to be treated with aheavily diluted liquor containing the active substance, or to achievethe modification by spraying on a heavily diluted aqueous formulation.In this connection, it is often advantageous to combine the modificationof the surfaces of the materials to be treated with a washing, cleaningand/or care or impregnation of the surface.

[0116] Suitable textile materials are all types of fiber fabrics,coverings and coatings, it being possible to treat both synthetic fibersand also natural fibers and modified natural fibers. Of particularsuitability are textiles of cotton fabric, modified cotton, such as, forexample, viscose, cotton blend, such as, for example, cotton/polyesterblend and cotton/polyamide blend and textiles made of finished fabricsor fibers. Other types of preferably treated textile surfaces are, forexample, carpets, furniture covers and decorations.

[0117] Further surfaces to be treated with preference with nanoparticlesaccording to the invention are all types of smooth and rough leathers.Of particular interest is the soil repellant modification of roughleather surfaces (e.g. made of suede) of leather clothing, shoes andfurniture.

[0118] Further surfaces to be treated preferably with nanoparticlesaccording to the invention are floor coverings made of plastics, suchas, for example, linoleum or PVC.

[0119] The modification of the surfaces of the abovementioned materialsconsists primarily in a soil repellant action as the result of thetreatment with the cationically modified hydrophilic nanoparticlesaccording to the invention. This means easier soil release during asubsequent washing, rinsing or cleaning operation. However, furthereffects can arise as well, such as, for example, a reduction in soiladhesion, protection against chemical or mechanical influences ordamage, improvement in the structural retention of fibers, improvementin the shape and structural retention of fabrics, a reduction in staticcharging, and an improvement in the feel.

[0120] The concentration of the hydrophilic nanoparticles during use ina rinse or care bath, in the laundry detergent liquor or in the cleaningbath is generally 0.0002 to 1.0% by weight, preferably 0.0005 to 0.25%by weight, particularly preferably 0.002 to 0.05% by weight.

[0121] Treatment of the respective surfaces is carried out withcationically modified hydrophilic nanoparticles according to theinvention from aqueous liquors or rinse or spray formulations whichcomprise, for example, 2.5 to 300 ppm, preferably 5 to 200 ppm and inparticular 10 to 100 ppm of one or more cationic polymers and/or 1 to 6mmol/l, preferably 1.5 to 4 mmol/l of one or more water-soluble salts ofdivalent metals, in particular salts of Ca, Mg or Zn and/or 0.05 to 2mmol/l, preferably 0.1 to 0.75 mmol/l of one or more water-soluble Alsalts and/or 1 to 600 ppm, preferably 10 to 300 ppm, of cationicsurfactants.

[0122] If cationically modified nanoparticles according to the inventionare used as additive, it is possible to dispense completely or partiallywith the addition of further cationic polymers, polyvalent metal ions orcationic surfactants.

[0123] The rinse liquor or the formulation to be sprayed on is usuallyprepared by diluting concentrated formulations with water orpredominantly aqueous solvents. If this dilution is carried out withwater which comprises at least 1.0 mmol of Ca²⁺ and/or Mg²⁺, preferablyat least 1.5 mmol/l, particularly preferably at least 2.0 mmol/l, thetreatment with dispersions of the hydrophilic nanoparticles can also becarried out without the addition of cationic polymers, polyvalent metalions and/or cationic surfactants.

[0124] Compositions according to the invention for the treatment ofsurfaces which are used in dilution with water may be solid or liquid.Solid compositions may be in the form of powders, granules or tabletsand, for use, are dissolved or dispersed in water, the nanoparticlesaccording to the invention being present in disperse distributionfollowing dilution.

[0125] The cationic modification of the hydrophilic nanoparticles ispreferably carried out prior to use in the aqueous treatmentcompositions. It may, however, also be carried out during thepreparation of the aqueous treatment compositions or during the use ofnon-cationically modified hydrophilic nanoparticles by, for example,mixing aqueous dispersions of the hydrophilic nanoparticles with theother constituents of the respective treatment composition in thepresence of cationic polymers, water-soluble salts of polyvalent metalsand/or cationic surfactants.

[0126] In a particular embodiment, the non-cationically modifiednanoparticles or formulations comprising these particles can also beadded directly to the rinse, wash or cleaning liquor if it is ensuredthat sufficient amounts of cationic polymers and/or polyvalent metalions and/or cationic surfactants are present in the liquor in dissolvedform. For example, it is possible to use the non-cationically modifiedhydrophilic nanoparticles or formulations comprising these particles inliquors with a content of cationic polymers of from 2.5 to 300 ppm, ofwater-soluble salts of Ca, Mg or Zn of more than 0.5 mmol/l, preferablymore than 1.0 mmol/l, particularly preferably more than 2.0 mmol/l. Ifcationic surfactants are used, they are used, for example, inconcentrations of from 50 to 1 000 ppm, preferably 75 to 500 ppm and inparticular from 100 to 300 ppm, in the aqueous liquor.

[0127] The hydrophilic, non-cationically modified nanoparticles orformulations comprising these nanoparticles can also be added to thewash liquor before, after or at the same time as a formulationcomprising cationic polymers, polyvalent metal ions and/or cationicsurfactants.

[0128] The present invention also provides a composition for the soilrelease treatment of surfaces of textile or nontextile materials,comprising:

[0129] a) 0.05 to 40% by weight of hydrophilic nanoparticles,

[0130] b) 0 to 30% by weight of one or more cationic polymers, cationicsurfactants and/or water-soluble salts of Mg, Ca, Zn or Al,

[0131] c) 0 to 20% by weight of acid,

[0132] d) 0 to 80% by weight of customary additives, such as bases,inorganic builders, organic cobuilders, further surfactants, polymericcolor transfer inhibitors, polymeric antiredeposition agents, furthersoil release polymers different from a), enzymes, complexing agents,corrosion inhibitors, waxes, silicone oils, light protection agents,dyes, nonaqueous solvents, extenders, hydrotropic agents, thickenersand/or alkanolamines, and

[0133] e) 0 to 99.95% by weight of water.

[0134] In are embodiment, the compositions according to the inventioncomprise 0.01 to 10% by weight of acid. In another embodiment, thecompositions according to the invention comprise 0.01 to 40% by weightof customary additives. In a further embodiment, the compositionsaccording to the invention comprise 50 to 95% by weight of water.

[0135] Compositions according to the invention for the treatment ofsurfaces which are used in dilution with water can, for example, havethe following composition:

[0136] (a) 0.1 to 40% by weight of hydrophilic nanoparticles,

[0137] (c) 0 to 20% by weight of acid, and

[0138] (d) 0.01 to 80% by weight of customary additives, such as acids,bases, inorganic builders, organic cobuilders, surfactants, polymericcolor transfer inhibitors, polymeric antiredeposition agents, furthersoil release polymers different from (a), enzymes, perfume substances,complexing agents, corrosion inhibitors, waxes, silicone oils, lightprotection agents, dyes, nonaqueous solvents, hydrotropic agents,thickeners and/or alkanolamines.

[0139] Preferred compositions according to the invention for thetreatment of surfaces to be used in dilution with water have thefollowing composition:

[0140] (a) 0.1 to 40% by weight of hydrophilic nanoparticles

[0141] (b) 0.1 to 30% by weight of cationic polymers and/orwater-soluble salts of Mg, Ca, Zn or Al and/or cationic surfactants,

[0142] (c) 0 to 20% by weight of acid, and

[0143] (d) 0 to 80% by weight of customary additives, such as bases,inorganic builders, organic cobuilders, surfactants, polymeric colortransfer inhibitors, polymeric antiredeposition agents, further soilrelease polymers different from (a), enzymes, perfume substances,complexing agents, corrosion inhibitors, waxes, silicone oils, lightprotection agents, dyes, nonaqueous solvents, hydrotropic agents,thickeners and/or alkanolamines.

[0144] Further preferred compositions according to the invention for thetreatment of surfaces which are used in dilution with water have thefollowing composition:

[0145] (a) 0.1 to 40% by weight of hydrophilic nanoparticles,

[0146] (b) 0.1 to 10% by weight of acid, and

[0147] (d) 0 to 80% by weight of customary additives, such as bases,inorganic builders, organic cobuilders, surfactants, polymeric colortransfer inhibitors, polymeric antiredeposition agents, further soilrelease polymers different from (a), enzymes, perfume substances,complexing agents, corrosion inhibitors, waxes, silicone oils, lightprotection agents, dyes, nonaqueous solvents, hydrotropic agents,thickeners and/or alkanolamines.

[0148] Particularly preferred compositions according to the inventionfor the treatment of surfaces which are used in dilution with water havethe following composition:

[0149] (a) 0.1 to 40% by weight of hydrophilic nanoparticles,

[0150] (b) 0.01 to 30% by weight of cationic polymers, water-solublesalts of Mg, Ca, Zn or Al and/or cationic surfactants

[0151] (c) 0.1 to 10% by weight of acid, and

[0152] (d) 0.01 to 80% by weight of customary additives, such as bases,inorganic builders, organic cobuilders, further surfactants, polymericcolor transfer inhibitors, polymeric antiredeposition agents, furthersoil release polymers different from (a), enzymes, perfume substances,complexing agents, corrosion inhibitors, waxes, silicone oils, lightprotection agents, dyes, nonaqueous solvents, hydrotropic agents,thickeners and/or alkanolamines, and

[0153] Liquid compositions are in the form of dispersions, where thedispersions may also be completely transparent if very smallnanoparticles according to the invention are used or their concentrationis very low. Liquid compositions according to the invention have a pHbelow 6.5, preferably below 5.5, particularly preferably below 4.5.

[0154] Liquid compositions for the soil release treatment of surfaceswhich are used in dilution with water can also have the followingcomposition:

[0155] (a) 0.1 to 40% by weight of hydrophilic nanoparticles,

[0156] (c) 0.1 to 10% by weight of acid,

[0157] (d) 0.01 to 40% by weight of at least one customary additive,such as bases, inorganic builders, organic cobuilders, surfactants,polymeric color transfer inhibitors, polymeric antiredeposition agents,further soil release polymers different from (a), enzymes, perfumesubstances, complexing agents, corrosion inhibitors, waxes, siliconeoils, light protection agents, dyes, nonaqueous solvents, hydrotropicagents, thickeners and/or alkanolamines.

[0158] (e) 50-95% by weight of water

[0159] where the pH of the composition is from 1 to 6.5.

[0160] Preferred liquid compositions for the soil release treatment ofsurfaces which are used in dilution with water can also have thefollowing composition:

[0161] (a) 0.1 to 40% by weight of hydrophilic nanoparticles,

[0162] (b) 0.01 to 30% by weight of cationic polymers, water-solublesalts of Mg, Ca, Zn or Al and/or cationic surfactants,

[0163] (c) 0.1 to 10% by weight of acid,

[0164] (d) 0.01 to 40% by weight of at least one customary additive,such as bases, inorganic builders, organic cobuilders, surfactants,polymeric color transfer inhibitors, polymeric antiredeposition agents,further soil release polymers different from (a), enzymes, perfumesubstances, complexing agents, corrosion inhibitors, waxes, siliconeoils, light protection agents, dyes, nonaqueous solvents, hydrotropicagents, thickeners and/or alkanolamines,

[0165] (e) 50-95% by weight of water

[0166] where the pH of the composition is from 1 to 6.5.

[0167] In the formulations described above, the component (b) can, forexample, have the following composition:

[0168] (b1) 0.01 to 10% by weight of cationic polymers and/or

[0169] (b2) 0.01 to 30% by weight of water-soluble salts of Mg, Ca, Znor Al and/or

[0170] (b3) 0.01 to 30% by weight of cationic surfactants,

[0171] in each case based on the total weight of the composition, wherethe sum of (b1) to (b3) is at most 30% by weight.

[0172] Suitable acids (c) are mineral acids, such as sulfuric acid,hydrochloric acid or phosphoric acid, or organic acids, such ascarboxylic acids or sulfonic acids, strong mineral acids and sulfonicacids being used either dilute in a small amount below 5% by weight oras partially neutralized acidic salts. Preference is given to usingC₁-C₃-monocarboxylic acids, C₂-C₁₈-dicarboxylic acids andC₆-C₁₈-tricarboxylic acids. In particular, formic acid, acetic acid,lactic acid, oxalic acid, succinic acid, C₃-C₁₄-alkylsuccinic acid,C₃-C₁₄-alkenylsuccinic acids, maleic acid, adipic acid, malic acid,tartaric acid, butanetetracarboxylic acid and citric acid are used.

[0173] Soil release laundry after-treatment and laundry carecompositions comprise, for example,

[0174] (a) 0.1 to 30% by weight of hydrophilic nanoparticles,

[0175] (b) 0.1 to 10% by weight of cationic polymers, water-solublesalts of Mg, Ca, Zn or Al and/or cationic surfactants,

[0176] (c) 0.05 to 20% by weight of a carboxylic acid, such as formicacid, citric acid, adipic acid, succinic acid, oxalic acid or mixturesthereof,

[0177] (d) 0 to 10% by weight of further customary ingredients, such asperfume, silicone oil, light protection agents, dyes, complexing agents,antiredeposition agents, further soil release polymers different from(a), color transfer inhibitors, nonaqueous solvents, hydrotropic agents,thickeners and/or alkanolamines and

[0178] (e) 30 to 99.65% by weight of water.

[0179] Preferred soil release laundry after-treatment and laundry carecompositions comprise

[0180] (a) 1 to 30% by weight of hydrophilic nanoparticles,

[0181] (b) 0.1 to 30% by weight of cationic polymers and/orwater-soluble salts of Mg, Ca, Zn and or Al and/or cationic surfactants,

[0182] (c) 1 to 15% by weight of a carboxylic acid, such as formic acid,citric acid, adipic acid, succinic acid, oxalic acid or mixturesthereof,

[0183] (d) 0 to 10% by weight of at least one other customaryingredient, such as perfume, silicone oil, light protection agents,dyes, complexing agents, antiredeposition agents, soil releasepolyesters, color transfer inhibitors, nonaqueous solvents, hydrotropicagents, thickeners and/or alkanolamines and

[0184] (e) 15 to 97.9% by weight of water.

[0185] The component (b) can, for example, consist of

[0186] (b1) 0.1 to 10% by weight of cationic polymers and/or

[0187] (b2) 0.1 to 30% by weight of water-soluble salts of Mg, Ca, Znand/or Al, where the content of water-soluble salts of aluminum is notmore than 10% by weight, and/or

[0188] (b3) 0.1 to 30% by weight of cationic surfactants,

[0189] in each case based on the total weight of the laundryafter-treatment or laundry care composition, where the sum of thecomponents (b 1) to (b3) is 0.1 to 30% by weight.

[0190] The component (b2) can, for example, consist of 0.1 to 30% byweight of water-soluble salts of Mg, Ca and/or Zn and/or 0.1 to 10% byweight of water-soluble salts of aluminum, based on the total weight ofthe laundry after-treatment or laundry care composition.

[0191] A further use form of the cationically modified hydrophilicnanoparticles according to the invention consists in spraying diluteaqueous formulations onto the surface to be treated. This can be carriedout in the home or in commercial use by spraying using a spray bottle oran automatic spraying device. The formulations suitable for this purposehave, for example, the following compositions:

[0192] (a) 0.005 to 2% by weight of hydrophilic nanoparticles,

[0193] (b) 0.0005 to 1% by weight of cationic polymers and/orwater-soluble salts of Mg, Ca, Zn and/or Al and/or cationic surfactants,

[0194] (c) 0 to 10% by weight of customary additives, such as bases,inorganic builders, organic cobuilders, surfactants, polymeric colortransfer inhibitors, polymeric antiredeposition agents, soil releasepolymers different from (a), enzymes, perfume substances, complexingagents, corrosion inhibitors, waxes, silicone oils, light protectionagents, dyes, solvents, hydrotropic agents, thickeners and/oralkanolamines.

[0195] (d) 87-99.9945% by weight of water,

[0196] where the pH of the composition is from 1 to 6.5.

[0197] Customary additives used in formulations according to theinvention are the additives used in washing compositions, cleaningcompositions and textile afterrinse compositions described, for example,in “Ullmanns Encyclopedia of Industrial Chemistry, Sixth Edition, 2000,Electronic Version 2.0”.

[0198] In particular, suitable surfactants and cobuilders are:

[0199] anionic surfactants, in particular:

[0200] (fatty) alcohol sulfates of (fatty) alcohols having 8 to 22,preferably 10 to 18, carbon atoms, e.g. C₉- to C₁₁-alcohol sulfates,C₁₂- to C₁₄-alcohol sulfates, C₁₂-C₁₈-alcohol sulfates, lauryl sulfate,cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate andtallow fatty alcohol sulfate;

[0201] sulfated alkoxylated C₈- to C₂₂-alcohols (alkyl ether sulfates);compounds of this type are prepared, for example, by firstlyalkoxylating a C₈- to C₂₂-alcohol, preferably a C₁₀- to C₁₈-alcohol,e.g. a fatty alcohol, and then sulfating the alkoxylation product.Ethylene oxide is preferably used for the alkoxylation;

[0202] linear C₈- to C₂₀-alkylbenzenesulfonates (LAS), preferably linearC₉- to C₁₋₃-alkyl-benzenesulfonates and -alkyltoluenesulfonates,

[0203] alkanesulfonates, such as C₈- to C₂₄-alkanesulfonates, preferablyC₁₀- to C₁₈-alkane-sulfonates

[0204] soaps, such as, for example, the Na and K salts of C₈- toC₂₄-carboxylic acids.

[0205] Said anionic surfactants are added to the washing compositionpreferably in the form of salts. Suitable cations in these salts arealkali metal ions, such as sodium, potassium and lithium and ammoniumions, such as hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium.

[0206] Nonionic surfactants, in particular:

[0207] alkoxylated C₈- to C₂₂-alcohols, such as fatty alcoholalkoxylates or oxo alcohol alkoxylates. These may be alkoxylated withethylene oxide, propylene oxide and/or butylene oxide. Surfactants whichmaybe used here are all alkoxylated alcohols, which contain at least twoadducted molecules of one of the abovementioned alkylene oxides. Blockpolymers of ethylene oxide, propylene oxide and/or butylene oxide aresuitable, or addition products which contain said alkylene oxides inrandom distribution. The nonionic surfactants contain, per mole ofalcohol, generally 2 to 50, preferably 3 to 20 mol, of at least onealkylene oxide. They preferably contain ethylene oxide as alkyleneoxide. The alcohols preferably have 10 to 18 carbon atoms. Depending onthe type of alkoxylation catalyst used in the preparation, thealkoxylates have a broad or narrow alkylene oxide homolog distribution;

[0208] alkylphenol alkoxylates, such as alkylphenol ethoxylates havingC₆- to C₁₄-alkyl chains and 5 to 30 alkylene oxide units;

[0209] alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbonatoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5,glucoside units;

[0210] N-alkylglucamides, fatty acid amide alkoxylates, fatty acidalkanolamide alkoxylates, and block copolymers of ethylene oxide,propylene oxide and/or butylene oxide.

[0211] Suitable inorganic builders are, in particular:

[0212] crystalline or amorphous alumosilicates having ion-exchangingproperties, such as, in particular, zeolites. Suitable zeolites are, inparticular, zeolites A, X, B, P, MAP and HS in their Na form or in formsin which Na is partially replaced by other cations such as Li, K, Ca,Mg, or ammonium;

[0213] crystalline silicates, such as, in particular, disilicates orphyllosilicates, e.g. δ-Na₂Si₂O₅ or β-Na₂Si₂O₅. The silicates can beused in the form of their alkali metal, alkaline earth metal or ammoniumsalts, preferably as Na, Li and Mg silicates;

[0214] amorphous silicates, such as, for example, sodium metasilicate oramorphous disilicate;

[0215] carbonates and hydrogencarbonates; these can be used in the formof their alkali metal, alkaline earth metal or ammonium salts.Preference is given to Na, Li and Mg carbonates or hydrogencarbonates,in particular sodium carbonate and/or sodium hydrogencarbonate;

[0216] polyphosphates, such as, for example, pentasodium triphosphate;

[0217] Suitable organic cobuilders are, in particular, low molecularweight, oligomeric or polymeric carboxylic acids.

[0218] Suitable low molecular weight carboxylic acids are, for example,citric acid, hydrophobically modified citric acid, such as, for example,agaric acid, malic acid, tartaric acid, gluconic acid, glutaric acid,succinic acid, imidodisuccinic acid, oxydisuccinic acid,propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids andamino-polycarboxylic acids, such as, for example, nitrilotriacetic acid,β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediaceticacid, isoserinediacetic acid, N-(2-hydroxyethyl)iminodiacetic acid,ethylenediaminedisuccinic acid and methyl- and ethylglycinediaceticacid;

[0219] suitable oligomeric or polymeric carboxylic acids are, forexample, homopolymers of acrylic acid, oligomaleic acids, copolymers ofmaleic acid with acrylic acid, methacrylic acid, C₂-C₂₂-olefins, suchas, for example, isobutene or long-chain α-olefins, vinyl alkyl etherswith C₁-C₈-alkyl groups, vinyl acetate, vinyl propionate, (meth)acrylicesters of C₁-C₈-alcohols and styrene. Preference is given to using thehomopolymers of acrylic acid and copolymers of acrylic acid with maleicacid. Also suitable are polyaspartic acids as organic cobuilders. Theoligomeric and polymeric carboxylic acids are used in acid form or assodium salt.

[0220] The invention is illustrated by the examples below.

EXAMPLES

[0221] Dispersions

[0222] Examples of typical anionic dispersions which can be processed bymixing with cationic polymers, water-soluble salts of polyvalent metalsand/or cationic surfactants, and other components to give rinse,cleaning or care compositions are the dispersions 1 to 3 described belowwhose dispersed particles, upon dynamic light scattering, can in eachcase be observed as discrete particles with the given average particlediameter.

[0223] With the nanoparticles to be used according to the invention, amuch higher soil release action is achieved particularly on cotton andcellulose fibers than with known processes.

[0224] The particle size distribution was measured using an “Autosizer2C” from Malvern, GB. Measurement was carried out at 23° C. Unlessotherwise stated, solutions are aqueous solutions. The designation pphmused in the examples means parts by weight based on 100 parts by weightof total monomers.

[0225] Dispersion 1

[0226] 66.8 g of an oxidatively degraded starch with a carboxylatedegree of substitution of from 0.03 to 0.04 and a K value of 34(determined in accordance with DIN 53726, Amylex 15 from Südstärke) and726 g of water are introduced into a polymerization vessel fitted withstirrer, reflux condenser, metering devices and equipment for workingunder a nitrogen atmosphere, and are heated with stirring over 25minutes to a temperature of 85° C. 0.2 g of a 25% strength by weightaqueous calcium acetate solution and 10 g of a 1% strength by weightcommercially available enzyme solution (alpha-amylase, Termamyl 120 Lfrom Novo Nordisk) are then added. After 15 minutes, the enzymaticstarch degradation is stopped by adding 6 g of glacial acetic acid. 16.8g of a 1% strength by weight aqueous iron(II)sulfate solution are alsoadded. The temperature of the reaction mixture is maintained at 85° C.At this temperature, a mixture of 55 g of ethyl acrylate, 77.5 g ofmethacrylic acid and 17 g of acrylic acid is then added over the courseof 90 minutes. The initiator feed starts at the same time as the monomerfeed. Over the course of 105 minutes, 42 g of a 15% strength by weighthydrogen peroxide solution are added. After the total amount ofinitiator has been added, the mixture is cooled to 50° C. 0.3 g of a 70%strength by weight tertiary-butyl hydroperoxide solution is then meteredin over the course of 15 minutes, and the mixture is after-stirred for30 minutes. The mixture is then cooled to room temperature, giving adispersion with a solids content of 21% by weight, an average particlediameter of the dispersed particles of 254 nm and a filtration residueof 0.3 g, based on the total mixture.

[0227] Dispersion 2

[0228] 8 g of a 2.5% strength by weight sodium peroxydisulfate solutionas initiator feed, 4 g of a 15% strength by weight sodium lauryl sulfatesolution and 841 g of water are introduced into a glass reactor providedwith anchor stirrer, thermometer, gas inlet pipe, dropping funnel andreflux condenser, and the mixture is heated with stirring in a heatingbath, the air simultaneously being displaced by the introduction ofnitrogen. When the heating bath has reached the preset temperature of75° C., the introduction of nitrogen is interrupted and an emulsionconsisting of 15 g of a 15% strength by weight sodium lauryl sulfatesolution, 266 ml of water, 72 g of ethyl acrylate, 106 g of methacrylicacid and 22 g of acrylic acid is added dropwise to the initial chargeover the course of 2 hours. When the addition is complete the mixture isafterpolymerized at 75° C. for 1 hour. The mixture is then cooled toroom temperature and, during cooling, 0.5 g of a 30% strength by weighthydrogen peroxide solution is added immediately, and a solutionconsisting of 0.2 g of ascorbic acid, 0.2 g of iron(II)sulfate and 19.8g of water is added over 15 minutes. This gives a dispersion with asolids content of 15% by weight, a particle diameter of 100 nm, a pH of3 and a filtration residue of 0.5 g, based on the total mixture.

[0229] Dispersion 3

[0230] 8 g of a 2.5% strength by weight sodium peroxydisulfate solutionas initiator feed, 4 g of a 15% strength by weight sodium lauryl sulfatesolution and 841 g of water are introduced into a glass reactor providedwith anchor stirrer, thermometer, gas inlet pipe, dropping funnel andreflux condenser, and the mixture is heated with stirring in a heatingbath, the air simultaneously being displaced by the introduction ofnitrogen. When the heating bath has reached the preset temperature of75° C., the introduction of nitrogen is interrupted and an emulsionconsisting of 15 g of a 15% strength by weight sodium lauryl sulfatesolution, 266 ml of water, 52 g of ethyl acrylate, 126 g of methacrylicacid and 22 g of acrylic acid is added dropwise to the initial chargeover the course of 2 hours. When the addition is complete the mixture isafterpolymerized at 75° C. for 1 hour. The mixture is then cooled toroom temperature and, during cooling, 0.5 g of a 30% strength by weighthydrogen peroxide solution is added immediately, and a solutionconsisting of 0.2 g of ascorbic acid, 0.2 g of iron(II)sulfate and 19.8g of water is added over 15 minutes. This gives a dispersion with asolids content of 15% by weight, a particle diameter of 100 nm, a pH of3 and a filtration residue of 0.6 g, based on the total mixture.

[0231] Washing Experiments

[0232] To test the soil release properties of afterrinse formulationscontaining nanoparticles according to the invention compared withafterrinse formulations of the prior art, the following washingexperiments were carried out:

Example 1

[0233] Dispersion 1 was diluted with deionized water of pH 4 to aconcentration of 2 000 ppm and metered, with stirring, into the sameamount of a solution of 200 ppm of high molecular weightpolyethyleneimine of molar mass 1 000 000 in deionized water of pH 4.The pH was adjusted using 0.1 N HCl.

[0234] The resulting dilute dispersion was used as afterrinse liquor.

Comparative Example 1

[0235] Dispersion 1 was diluted with deionized water of pH 4, adjustedusing 0.1 N HCl, to a concentration of 1 000 ppm and used as afterrinseliquor.

Comparative Example 2

[0236] The aqueous solution of a copolymer as in example 1 of U.S. Pat.No. 3,836,496 of methacrylic acid and ethyl acrylate in the weight ratio66.6:33.3 was diluted to a concentration of 1 000 ppm and adjusted to apH of 4 using 1 N HCl. This solution was used as afterrinse liquor.

Example 2

[0237] Dispersion 2 was diluted with water which contained 3.0 mmol/l ofCaCl₂ in dissolved form and had been adjusted to a pH of 4 using 0.1 NHCl, to a concentration of 1 000 ppm. The resulting dilute dispersionwas used as afterrinse liquor.

Comparative Example 3

[0238] A solution of a copolymer with a polymer content of 1 000 ppm asin example 1 of U.S. Pat. No. 3,993,830 of methacrylic acid and ethylacrylate in the weight ratio 66.6:33.3 was prepared in water of pH 4,adjusted using 0.1 N HCl, which contained 3.0 mmol/l of calcium chloridein dissolved form. This solution was used as afterrinse liquor.

Comparative Example 4

[0239] Dispersion 2 was diluted with deionized water of pH 4, adjustedusing 0.1 N HCl, to a concentration of 1 000 ppm and used as afterrinseliquor.

Example 3

[0240] 33.3 g of dispersion 3 were diluted with 1.25 M aqueous formicacid to 50 g. 1.4 g of calcium chloride was diluted with 1.25 M aqueousformic acid to 50 g. The dispersion was mixed with the calcium chloridesolution with stirring. The resulting formulation contained 5.0% byweight of hydrophilic nanoparticles and 126 mmol/l of calcium ions. Forthe afterrinse liquor, 16 g of the formulation were used per liter ofwater containing 0.5 mmol/l of calcium chloride.

Comparative Example 5

[0241] 33.3 g of the dispersion from example 3 were diluted with 1.25 Mformic acid to 100 g. The resulting formulation contained 5.0% ofnanoparticles and no calcium ions. For the afterrinse liquor, 16 g ofthe formulation were used per liter of water containing 0.5 mmol/l ofcalcium chloride.

[0242] In separate experiments, two 2.5 g of cotton fabric orpolyester/cotton (50:50) blend (test fabric) in each case were washedwith 5 g of ballast fabric (equal parts of cotton and cotton/polyesterblend) using a granular household heavy-duty detergent (Ariel Futur),rinsed with tap water and afterrinsed with the afterrinse liquors fromexamples 1 to 3. The test fabrics were then dried and soiled.

[0243] In a first experimental series, lipstick composition was used assoiling. It was applied using a brush and a stencil in a circle 4 cm indiameter.

[0244] In a second experimental series, spent engine oil was used assoiling. It was applied by dripping 0.3 g of the oil onto the horizontalfabric.

[0245] The reflectance of the soiled fabrics was determined prior towashing at 460 nm (in % reflectance). The fabrics were then washed againusing the heavy-duty detergent (Ariel Futur) with addition of 15 g ofballast fabric (in equal parts of cotton and cotton/polyester blend). Toevaluate the soil release effect, the reflectance of the soiled fabricswas measured after washing at 460 nm (in % reflectance), and thereflectance difference ΔR was determined from the reflectance valuesbefore and after washing. The values for both fabrics of one experimentwere averaged and rounded to whole numerical values.

[0246] Washing conditions: Prewash: Washing machine: Launder-0-meterPrewash temperature: 20° C. Prewash time: 15 min Liquor ratio: 25 Mainwash: Wash temperature: 40° C. Detergent: Ariel Futur Detergent dosing:3.5 g/l Wash time: 30 min Water hardness: 3 mmol/l Ca/Mg ratio: 3:1Liquor ratio: 12.5

[0247] TABLE 1 Washing experiments with lipstick composition as soilingComparative Comparative Comparative Comparative Comparative Example 1Example 2 Example 3 example 1 example 2 example 3 example 4 example 5 Δ45 46 42 30 31 33 30 36 reflectance (cotton) Δ 56 57 51 41 44 45 43 45reflectance (blend)

[0248] TABLE 2 Washing experiments with dirty engine oil as soilingComparative Comparative Comparative Comparative Comparative Example 1Example 2 Example 3 example 1 example 2 example 3 example 4 example 5 Δ38 42 40 29 29 30 28 31 reflectance (cotton) Δ 31 35 33 21 24 25 25 27reflectance (blend)

[0249] The comparison of example 1 with the comparative examples 1 and 2shows that in the case of rinsing with nanoparticles in water in theabsence of hardness ions, a good soil release action only arises if acationic polymer is present. The dissolved acrylate copolymer as in U.S.Pat. No. 3,836,496 exhibits no effect on the cotton/polyester blend atthe same use concentration. The comparison of example 2 with thecomparative examples 3 and 4 shows that in the case of a rinse withnanoparticles according to the invention in water in the presence of 3mmol/l of Ca ions, a very good soil release action arises, whereas thisis not observed in the absence of Ca ions. With the dissolved polymer asin U.S. Pat. No. 3,993,830, no satisfactory effect is achieved even inthe presence of 3.0 mmol of Ca ions.

[0250] The comparison of example 3 with comparative example 5 shows thatif the concentration of calcium ions is lower, as arises, for example,in the tap water in regions with soft water, only the formulationaccording to the invention with additional calcium ions brings about agood action.

1-14. (Canceled).
 15. A process for the soil release treatment ofsurfaces of textile and nontextile materials, in which cationicallymodified hydrophilic nanoparticles based on uncrosslinked polymers of(a) 60 to 100% by weight of one or more carboxyl-containingethylenically unsaturated monomers or salts thereof, (b) 0 to 40% byweight of one or more water-insoluble monoethylenically unsaturatedmonomers, (c) 0 to 25% by weight of one or more sulfonic acid- and/orphosphonic acid-containing monomers or salts thereof, (d) 0 to 30% byweight of one or more water-soluble nonionic monomers are applied to thesurface of the materials from an aqueous dispersion, where thedispersion of the hydrophilic nanoparticles can be stabilized withanionic, nonionic and/or betainic emulsifiers and/or protectivecolloids, and where the hydrophilic nanoparticles have a particle sizeof from 10 nm to 2 μm and have been cationically modified by coatingtheir surface with one or more cationic polymers, one or more polyvalentmetal ions and/or one or more cationic surfactants.
 16. A process asclaimed in claim 15, wherein the aqueous dispersion comprises 0.0002 to1% by weight of hydrophilic nanoparticles.
 17. A process as claimed inclaim 15, wherein the pH of the aqueous dispersion is from 1 to 6.5. 18.A process as claimed in claim 15, wherein the cationic polymers arechosen from the group consisting of polymers containing vinylamineunits, polymers containing vinylimidazole units, polymers containingquaternary vinylimidazole units, imidazole/epichlorohydrin condensates,uncrosslinked polyamidoamines, uncrosslinked polyamidoamines graftedwith ethyleneimine, polyethyleneimines, alkoxylated polyethyleneimines,uncrosslinked polyethyleneimines, amidated polyethyleneimines, alkylatedpolyethyleneimines, polyamines, amine/epichlorohydrin polycondensates,alkoxylated polyamines, polyallylamines, polydimethyldiallylammoniumchlorides, polymers containing basic (meth)acrylamide or (meth)acrylicester units, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units, and lysine condensates.
 19. A process asclaimed in claim 15, wherein the polyvalent metal cations are chosenfrom the group consisting of Mg²⁺, Ca²⁺, Ba²⁺, Al³⁺ and Zn²⁺.
 20. Aprocess as claimed in claim 15, wherein the cationic surfactants arechosen from the group consisting of C₇-C₂₅-alkylamine,C₇-C₂₅-alkylammonium, di(C₇-C₂₅)alkylammonium, C₇-C₂₅-alkyl ester quatand C₇-C₂₅-alkylimidazolinium compounds.
 21. Cationically modifiedhydrophilic nanoparticles based on uncrosslinked polymers of (a) 75 to95% by weight of one or more carboxyl-containing ethylenicallyunsaturated monomers or salts thereof, (b) 5 to 25% by weight of one ormore water-insoluble monoethylenically unsaturated monomers, (c) 0, 1 to5% by weight of one or more sulfonic acid- and/or phosphonicacid-containing monomers or salts thereof, (d) 0 to 30% by weight of oneor more water-soluble nonionic monomers, where the hydrophilicnanoparticles have a particle size of from 10 nm to 2 μm and have beencationically modified by coating their surface with one or more cationicpolymers, one or more polyvalent metal ions and/or one or more cationicsurfactants.
 22. An aqueous dispersion of cationically modifiedhydrophilic nanoparticles based on uncrosslinked polymers of (a) 75 to95% by weight of one or more carboxyl-containing ethylenicallyunsaturated monomers or salts thereof, (b) 5 to 25% by weight of one ormore water-insoluble monoethylenically unsaturated monomers, (c) 0, 1 to5% by weight of one or more sulfonic acid- and/or phosphonicacid-containing monomers or salts thereof, (d) 0 to 30% by weight of oneor more water-soluble nonionic monomers, where the dispersion of thehydrophilic nanoparticles can be stabilized with anionic, nonanionicand/or betainic emulsifiers and/or protective colloids, and where thehydrophilic nanoparticles have a particle size of from 10 nm to 2 μm andhave been cationically modified by coating their surface with one ormore cationic polymers, one or more polyvalent metal ions and/or one ormore cationic surfactants.
 23. An aqueous dispersion as claimed in claim22, which comprises 0.001 to 50% by weight of hydrophilic nanoparticles.24. The use of hydrophilic nanoparticles or of cationically modifiedhydrophilic nanoparticles, as are defined in claim 15 as soil releaseadditive to rinse, care, washing and cleaning compositions.
 25. Acomposition for the soil release treatment of surfaces of textile ornontextile materials comprising a) 0.05 to 40% by weight of hydrophilicnanoparticles, as in claim 21, b) 0 to 30% by weight of one or morecationic polymers, cationic surfactants and/or water-soluble salts ofMg, Ca, Zn or Al, c) 0, 01 to 10% by weight of acid, d) 0 to 80% byweight of customary additives, such as bases, inorganic builders,organic cobuilders, further surfactants, polymeric color transferinhibitors, polymeric antiredeposition agents, soil release polymers,enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils,light protection agents, dyes, solvents, extenders, hydrotropic agents,thickeners and/or alkanolamines, e) 0 to 99.95% by weight of water. 26.A composition as claimed in claim 25, comprising b) 0.1 to 30% by weightof cationic polymers, cationic surfactants and/or water-soluble salts ofMg, Ca, Zn or Al.
 27. A composition as claimed in claim 25, comprisingd) 0.01 to 40% by weight of customary additives, e) 50 to 95% by weightof water.